EP0885872B1 - Procédé continu de fabrication de solutions aqueuses de sels alcalins d'acides arylacétiques. - Google Patents
Procédé continu de fabrication de solutions aqueuses de sels alcalins d'acides arylacétiques. Download PDFInfo
- Publication number
- EP0885872B1 EP0885872B1 EP98401244A EP98401244A EP0885872B1 EP 0885872 B1 EP0885872 B1 EP 0885872B1 EP 98401244 A EP98401244 A EP 98401244A EP 98401244 A EP98401244 A EP 98401244A EP 0885872 B1 EP0885872 B1 EP 0885872B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aqueous solution
- zone
- mixing
- introducing
- alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
Definitions
- alkaline salts of arylacetic acids are raw materials important to the chemical industry. They are very widely used for the synthesis of various pharmaceutical products. So the phenylacetates of sodium or potassium are synthetic intermediates for the penicillin G preparation.
- alkali salts of arylacetic acids can be precursors for the synthesis of arylacetic acids and their esters used in particular for the preparation of pharmaceutical products, dyes and perfumes.
- the methods commonly described for obtaining the alkaline salts of arylacetic acids consist in carrying out the alkaline hydrolysis of arylacetonitriles.
- This alkaline hydrolysis reaction is a slow reaction requiring efficient stirring means and long heating which, given the instability of arylacetonitriles to heat, is likely to lead to the formation of by-products lowering the yield and causing costly subsequent purification operations, prohibitive for a industrial process.
- Raw alkaline aqueous solutions as obtained previously, i.e. not purified, can be acidified to lead to arylacetic acids which must then be purified by distillation or crystallization.
- arylacetic acids can be prepared by direct acid hydrolysis of arylacetonitriles.
- Sulfuric acid is generally used, but its use has many drawbacks. Poor selectivity is noted due to the presence of by-products resulting in particular from the sulfonation of aromatic rings. In Consequently, the yields are low and in addition there are effluents such that ammonium sulphate difficult to recover without further treatment expensive.
- aqueous solutions of alkali salts of said arylacetic acids - obtained by acid hydrolysis of arylacetonitriles - can be obtained by neutralization of said arylacetic acids. But this way of operating is expensive considering that the preparation of said arylacetic acids by acid hydrolysis of arylacetonitriles is not very selective and also expensive.
- the Applicant has found a simple, continuous process for lead in a very short time to aqueous solutions of alkaline salts arylacetic acids by alkaline hydrolysis of arylacetonitriles do not all of these drawbacks and, moreover, provides pure arylacetic acids by simple acidification of said solutions.
- the aqueous alkali hydroxide solution MOH and arylacetonitrile (II) can be preheated to a temperature at least equal to 50 ° C and preferably at a temperature between 100 ° C and 130 ° C.
- the preheating temperatures of the identical reagents but we would not go beyond the scope of the invention if we used different reagent preheating temperatures.
- the mixing technique used in step a) must be adapted to carry out an intimate mixing of the reagents.
- contact time between the reagents is at most equal to 10 minutes, and preferably ranges from 0.01 seconds to 6 minutes.
- the weight concentration of MOH of aqueous solutions of alkali hydroxide can vary to a large extent. She is at least equal to 10% and, preferably, between 20% and 60%.
- the reaction medium obtained in step b), which is in the form of an alkaline aqueous solution comprising alkaline salt of an arylacetic acid and of the ammonia formed during the reaction, is introduced into a separation zone in which most of the ammonia is eliminated.
- the temperature and the pressures are preferably at most equal to those of step b).
- the ammonia recovered can be advantageously recovered in the form aqueous solutions.
- the alkaline aqueous solution of the alkali salt of arylacetic acid almost rid of its ammonia is introduced into an area of stripping in which the residual ammonia is removed.
- the solution is advantageously stripped with steam superheated, air or an inert gas such as nitrogen.
- the solution leaving the stripping zone of step d) is brought into contact in a mixing zone with a sufficient quantity of an arylacetic acid of formula: to neutralize any unused amount of alkaline hydroxide.
- arylacetic which can be optionally diluted in order to obtain a solution of alkali arylacetate having a weight concentration of alkali arylacetate suitable for its subsequent use and to obtain an alkaline salt solution arylacetic acid fully soluble at room temperature.
- This process is particularly applicable to the preparation of sodium or potassium phenylacetates, from phenylacetonitrile.
- the invention also relates to an installation for the manufacture of aqueous solutions of alkali salts of arylacetic acids.
- This installation shown schematically in Figure 1 comprises an enclosure (1) containing mixing means provided with a supply of arylacetonitrile (2) and supply in aqueous solution of alkali hydroxide (3), a line (4) for admitting the mixture into a reactor (5) comprising at least one empty vertical cylindrical tube (T), one line (6) for admitting the aqueous solution containing an alkaline salt arylacetic acid and ammonia in an enclosure (7) containing gas / liquid separation means, a pipe (8) for admitting the solution aqueous degassed in a stripping column (9), a pipe (10) of the stripped aqueous solution into an enclosure (11) containing mixing means provided with a neutralizing agent supply (12), a pipe (13) for admission into an enclosure (14) containing mixing means provided with a water supply (15), a pipe (16) of admission of the aqueous solution of the alkaline salt of arylacetic acid into a storage area (17) and vents (18) and (19).
- a reactor (5) comprising at least one empty vertical
- the mixing means contained in the enclosure (1) can be constituted by any device making it possible to obtain intimate contact of reagents.
- static mixers can include one or more identical or different mixing elements.
- These mixing elements may include pleated lamellas or an array of crossed blades, nested in each other.
- the reagents are introduced into (1) through the supplies (2) and (3). These reagents can be preheated by means not shown on the Figure 1.
- the mixture leaving (1) is transferred through line (4) into the reactor (5) preferably at its lower part.
- the tube (s) contained (have) loose packing such as Raschig rings, Pall rings, balls, an ordered packing.
- the number of tubes can vary widely. It is proportional to the productivity of aqueous solutions of alkaline acid salt arylacetic desired.
- the reactor (5) is provided with heating means not shown on Figure 1, such as heat transfer fluid, high pressure steam.
- heating means such as heat transfer fluid, high pressure steam.
- the aqueous solution, consisting mainly of ammonia and salt alkaline arylacetic acid, leaving the reactor (5) is conveyed by a line (6) in a gas / liquid separation zone consisting of a separator (7) which can be a large empty container in which the ammonia gas separates from the aqueous solution, in particular by expansion.
- the stripping means can be constituted by a stripping column (9) containing a loose packing consisting in particular of Raschig rings, Pall rings, packing ordered and at the base of which a stream of water vapor, air or of an inert gas.
- a stripping column 9 containing a loose packing consisting in particular of Raschig rings, Pall rings, packing ordered and at the base of which a stream of water vapor, air or of an inert gas.
- gas is eliminated by the vent (19) consisting mainly of steam, air or inert gas and residual ammonia.
- aqueous solution alkaline of arylacetic acid alkaline salt which is conveyed by a line (10) to a first mixing zone (11) consisting of preferably by static mixers as mentioned above.
- These mixers can be of the same type or different from those used in (1).
- This mixing zone (11) is supplied with an agent capable of neutralize any excess alkalinity through the supply line (12).
- the neutralized aqueous solution leaving (11) is transferred to a second mixing zone (14) via a pipe (13).
- This mixing zone (14) is also preferably made up by static mixers as mentioned above and which may be of the same type or different from those used in (1) and (11).
- this mixing zone is carried out (14) dilution of the aqueous solution of alkali salt of arylacetic acid with water which is introduced by (15).
- the aqueous solution thus diluted is transferred to a zone of storage (17) through the pipe (16).
- the mixing means contained in the enclosure (1) can be integrated into the reactor (5).
- the mixing means can be advantageously arranged at the bottom of said reactor (5) or directly inside the tube (s), these mixing means can be constituted by mixing elements such as those used in the static mixers as mentioned above.
- the process according to the present invention makes it possible to obtain, with a very high yield of alkali salt of arylacetic acid and an almost quantitative transformation of the corresponding arylacetonitrile, aqueous solutions of alkali salt of arylacetic acid pure and free of NH 3 .
- the method also has the advantage of being implemented by means of a simple installation, in particular devoid of any agitation system of the dynamic type which is likely to cause leaks and is costly in energy.
- the method according to the present invention allows great flexibility.
- the ammonia formed can be recovered in the form of directly marketable ammonia solutions.
- Aqueous solutions of arylacetic acid alkali salt can advantageously be precursors to obtain acids directly arylacetic by acidification.
- a tubular reactor formed from a stainless steel tube with a diameter is used 2.3 cm and 18 cm long and lined with Raschig rings leaving a useful volume of 36 ml.
- the tube is surrounded by a double envelope allowing its heating by means of an oil circulation.
- 0.25 mol / h (29.5 g / h) of phenylacetonitrile) is then introduced preheated to 100 ° C. and 0.30 mol / h of NaOH in the form of a 26% aqueous solution (46.1 g / h) also preheated to 100 ° C (20% excess) in the reactor maintained at 170 ° C under a regulated pressure of 8.10 5 Pa (8 bar).
- the residence time is 30 minutes.
- the flow leaving the reactor is recovered in a pressure vessel 5 atmospheric. After separation of a transitional phase corresponding to the soda initially present in the reactor, a stabilized regime is obtained aqueous solution of sodium phenylacetate, the composition of which is determined by potentiometric analysis and chromatographic analysis (organic extraction with a solvent). The duration of the steady-state test stabilized is 3h.
- the tube is surrounded by a double envelope allowing it to be heated at by means of an oil circulation.
- the reactor previously filled with an aqueous solution of sodium phenylacetate at 44% and placed under a nitrogen pressure of 3.10 5 Pa (3 bar) is heated to 150 ° C.
- 1.5 mol / h (176 g / h) of preheated phenylacetonitrile are then introduced at 100 ° C and 1.6 mol / h of NaOH in the form of a 5% aqueous solution (excess of 6.5%) in a mixing enclosure (by magnetic stirring) connected to the base of the reactor.
- the mixture is introduced into the reactor maintained at 150 ° C. under a regulated pressure of 3.10 5 Pa (3 bars) the residence time is 26 minutes.
- the flow leaving the reactor is recovered in a pressure vessel atmospheric. After separation of a transitional phase corresponding to the solution of sodium phenylacetate initially present in the reactor, obtains in stabilized regime an aqueous solution of sodium phenylacetate whose composition is determined by potentiometric analysis and analysis chromatographic (extraction of organics with a solvent). The duration of the test is 5h in steady state.
- Example 2 The same tubular reactor is used as in Example 2 but packed Raschig rings leaving a useful volume of 82 ml.
- the reactor previously filled with an aqueous solution of sodium phenylacetate at 44% and placed under a nitrogen pressure of 5 bars is heated to 150 ° C.
- the mixture is introduced into the reactor maintained at 150 ° C. under a regulated pressure of 6.10 5 Pa (6 bars), the residence time is 26 minutes.
- the flow leaving the reactor is recovered in a pressure vessel atmospheric. After separation of a transitional phase corresponding to the solution of sodium phenylacetate initially present in the reactor, obtains in stabilized regime an aqueous solution of sodium phenylacetate whose composition is determined by potentiometric analysis and analysis chromatographic (extraction of organics with a solvent). The duration of the test is 5h in steady state;
- FIG. 1 A device as shown in FIG. 1 is used.
- the mixture is introduced into a tubular reactor made of 316L stainless steel consisting of 6 tubes, each tube having a height equal to 3 m and a diameter equal to 2, 5 cm.
- Said tubes are previously filled with an aqueous solution of sodium phenylacetate and are maintained at 150 ° C (external heating with steam 12.10 5 Pa) under a pressure of 6 bars.
- the residence time in the reactor is 8.5 minutes.
- the flow leaving said reactor is introduced by (6) into a separator gas / liquid (7) consisting of a capacity of 316L stainless steel of 12 liters.
- the aqueous sodium phenylacetate solution leaving the separator which has been freed of its NH 3 after expansion at atmospheric pressure, has the following average composition: PhCH 2 CO 2 Na 55.2% NaOH 2.3% NH 3 1.1% H 2 O 41.4% with a residual amount of phenylacetonitrile less than 25 mg / kg.
- This solution is then introduced by (8) into a stripping column (9) of 6 theoretical plates constituted by an ordered packing in stainless steel.
- the stripping is carried out at a temperature of 120 ° C. with steam 2.10 5 Pa (2 bars).
- column head (19) leaves a stream consisting essentially of ammonia and water while the sodium phenylacetate solution almost completely rid of its ammonia (residual content less than 50 ppm) is extracted at the bottom of the column (9) and is introduced by (10) into a static mixer (11) of the SMXE type.
- this second static mixer (11) simultaneously introduced by (10) the solution from the stripping column and by (12) a stream a sufficient amount of phenylacetic acid ( ⁇ 3.7 kg / h) at 90 ° C to neutralize excess soda.
- the solution leaving the static mixer (11) is then introduced by (13) into a static mixer (14) identical to (11) at the same time as a stream of water introduced by (15) in order to obtain a aqueous solution of sodium phenylacetate having a concentration by weight in sodium phenylacetate of 44%.
- the duration of the steady-state test is 4 hours.
- the same device is used as for example 4.
- the mixture is introduced into the tubular reactor (5), the tubes of which are previously filled with a 40.8% potash solution and are kept at 150 °. C under a pressure of 6.10 5 Pa (6 bars).
- the residence time in the reactor is 10 minutes.
- this solution is then stripped in the column (9) to obtain a residual content of ammonia less than 50 mg / kg and then introduced into the static mixer (11) with a stream of a sufficient amount of phenylacetic acid ( ⁇ 1.9 kg / h) at 90 ° C to neutralize excess potash.
- the solution coming out of static mixer (11) is then introduced into the static mixer (14) together with a stream of water in order to obtain an aqueous solution of potassium phenylacetate having a weight concentration of 64% potassium phenylacetate.
- the duration of the steady-state test is 5 hours.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
PhCH2CO2Na | 55,2 % |
NaOH | 2,3 % |
NH3 | 1,1 % |
H2O | 41,4 % |
EXEMPLE N° | 4 | 5 | 6 | 7 |
Excès molaire de NaOH (en %) | 15,4 | 12,0 | 13,7 | 11,3 |
Zone de mélange : | ||||
- température (en °C) | 105 | 100 | 105,0 | 105 |
- temps de séjour (en seconde) | 0,05 | 0,05 | 0,07 | 0,05 |
Zone réactionneile: | ||||
- température (en °C) | 150 | 150 | 145 | 135 |
- temps de séjour (en minutes) | 8,5 | 8,5 | 12 | 8,5 |
Pression (en Pascal) | 6.105 | 9.105 | 9.105 | 1.106 |
Concentration moyenne de la solution aqueuse de phénylacétate de sodium en sortie dù séparateur gaz/liquide : | ||||
- en C6H5CH2CO2Na (en %) | 55,2 | 53,5 | 52,6 | 55,3 |
- en C6H5CH2CN (en ppm) | < 25 | <25 | <50 | <50 |
Conversion du phénylacétonitrile en phénylacétate de sodium (en %) | >99,9 | >99,9 | >99,9 | >99,9 |
Durée de l'essai en régime stabilisé (en h) | 4 | 5 | 5,5 | 3 |
PhCH2CO2K | 69,6 % |
KOH | 1,85 % |
NH3 | 0,65 % |
H2O | 27,9 % |
Claims (16)
- Procédé continu de préparation d'une solution aqueuse d'un sel alcalin d'acide arylacétique de formule : dans laquelle R représente un radical hydrocarboné aliphatique, linéaire ou ramifié ayant un nombre de carbone allant de 1 à 10, un atome d'halogène, un groupe alcoxy linéaire ou ramifié ayant un nombre de carbone allant de 1 à 6, un groupe phénoxy ; M représente un métal alcalin, n est un nombre allant de 0 à 5, et x est un nombre allant de 1 à 2 avec n + x inférieur ou égal à 6 ; par hydrolyse alcaline d'un arylacétonitrile de formule : R, n et x ayant les mêmes significations que dans la formule (I) selon la réaction ledit procédé étant caractérisé en ce qu'il consiste essentiellement :a) à mettre en contact dans une zone de mélange un arylacétonitrile (II) avec une solution aqueuse d'un hydroxyde alcalin MOH selon un rapport molaire MOH / (II) au moins égal à x,b) à introduire le mélange obtenu en a) dans une zone de réaction sous une pression supérieure ou égale à la pression atmosphérique et à maintenir ledit mélange dans ladite zone réactionnelle pendant une durée au plus égale à 60 minutes à une température comprise entre 100°C et 180°C,c) à transférer le milieu obtenu en b) dans une zone de séparation,d) à transférer le milieu obtenu en c) dans une zone de stripping,e) à mettre en contact la solution obtenue en d) avec un agent neutralisant qui est un acide arylacétique de formule dans une zone de mélange, puis,f) à récupérer une solution aqueuse d'un sel alcalin d'acide arylacétique pure,
- Procédé selon la revendication 1, caractérisé en ce que le temps de contact entre les réactifs dans la zone de mélange de l'étape a) est, au plus égal à 10 minutes.
- Procédé selon la revendication 2, caractérisé en ce que le temps de contact entre les réactifs dans la zone de mélange de l'étape a) est compris entre 0,01 seconde et 6 minutes.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le mélange obtenu dans l'étape a) est introduit dans une zone de réaction - étape b)- sous une pression comprise entre 2 bars absolus et 12 bars absolus et est maintenu dans ladite zone réactionnelle -pendant une durée comprise entre 5 minutes et 30 minutes à une température comprise entre 130°C et 160°C.
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le rapport molaire MOH/(II) est compris entre 1,05x et 1,20x.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la solution aqueuse d'un sel alcalin d'acide arylacétique obtenue dans l'étape e) est dilué avec de l'eau.
- Procédé selon l'une des revendications 1 à 6, caractérisé en ce que n est nul.
- Procédé selon l'une des revendications 1 à 7, caractérisé en ce que x = 1.
- Procédé selon l'une des revendications 1 à 8, caractérisé en ce que le métal alcalin est le sodium ou le potassium.
- Solution aqueuse de phénylacétate de sodium obtenue selon l'une quelconque des revendications 1 à 9.
- Solution aqueuse de phénylacétate de potassium obtenue selon l'une quelconque des revendications 1 à 9.
- Installation comprenant une enceinte (1) contenant des moyens de mélange munie d'une alimentation en arylacétonitrile (2) et d'une alimentation en solution aqueuse d'hydroxyde alcalin (3), une conduite (4) d'admission du mélange dans un réacteur (5) comprenant au moins un tube cylindrique (T) vertical vide, une conduite (6) d'admission de la solution aqueuse contenant un sel alcalin d'acide arylacétique et de l'ammoniac dans une enceinte (7) contenant des moyens de séparation gaz/liquide, une conduite (8) d'admission de la solution aqueuse dégazée dans une colonne de stripping (9), une conduite (10) d'admission de la solution aqueuse strippée dans une enceinte (11) contenant des moyens de mélange munie d'une alimentation en agent neutralisant (12), d'une conduite (13) d'admission dans une enceinte (14) contenant des moyens de mélange munie d'une alimentation (15) en eau, une conduite (16) d'admission de la solution aqueuse du sel alcalin d'acide arylacétique dans une zone de stockage (17) et des évents (18) et (19).
- Installation selon la revendication 12, caractérisée en ce que dans l'enceinte (1), le mélange est réalisé par un mélangeur statique.
- Installation selon la revendication 13, caractérisée en ce que le mélangeur statique comprend au moins un élément mélangeur comprenant des lamelles plissées ou un réseau de lames croisées, emboítées les unes dans les autres.
- Installation selon la revendication 12, caractérisée en ce que la colonne de stripping (9) contient un garnissage.
- Installation selon la revendication 12, caractérisée en ce que les moyens de mélange contenus dans les enceintes (11) et (14) sont des mélangeurs statiques.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9707440 | 1997-06-16 | ||
FR9707440A FR2764600B1 (fr) | 1997-06-16 | 1997-06-16 | Procede continu de fabrication de solutions aqueuses de sels alcalins d'acides arylacetiques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0885872A1 EP0885872A1 (fr) | 1998-12-23 |
EP0885872B1 true EP0885872B1 (fr) | 2001-11-21 |
Family
ID=9508022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98401244A Expired - Lifetime EP0885872B1 (fr) | 1997-06-16 | 1998-05-26 | Procédé continu de fabrication de solutions aqueuses de sels alcalins d'acides arylacétiques. |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0885872B1 (fr) |
JP (1) | JPH1171322A (fr) |
CN (1) | CN1203220A (fr) |
AT (1) | ATE209176T1 (fr) |
CA (1) | CA2238398A1 (fr) |
DE (1) | DE69803244T2 (fr) |
ES (1) | ES2167851T3 (fr) |
FR (1) | FR2764600B1 (fr) |
IN (1) | IN187756B (fr) |
PT (1) | PT885872E (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1300090C (zh) * | 2005-03-02 | 2007-02-14 | 杭州师范学院 | 一种芳基乙酸的制备方法 |
CN106278859B (zh) * | 2016-08-24 | 2019-03-12 | 河北诚信集团有限公司 | 一种高品质苯乙酸的生产工艺 |
CN113600119A (zh) * | 2021-08-04 | 2021-11-05 | 江苏聚双环新材料科技有限公司 | 自留分离式供料罐 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2817681A (en) * | 1954-12-20 | 1957-12-24 | Monsanto Chemicals | Arylacetic acids |
DE1909440A1 (de) * | 1968-03-18 | 1969-11-13 | Lummos Company | Verfahren zur Herstellung von aromatischen Carbonsaeuren |
US4031243A (en) * | 1975-07-03 | 1977-06-21 | Juste, S.A. Quimico-Farmaceutica | 2-(4-Isobutyl phenyl)butyric acid, salts thereof, and pharmaceutical compositions containing the same |
-
1997
- 1997-06-16 FR FR9707440A patent/FR2764600B1/fr not_active Expired - Fee Related
-
1998
- 1998-05-21 CA CA002238398A patent/CA2238398A1/fr not_active Abandoned
- 1998-05-26 AT AT98401244T patent/ATE209176T1/de not_active IP Right Cessation
- 1998-05-26 PT PT98401244T patent/PT885872E/pt unknown
- 1998-05-26 DE DE69803244T patent/DE69803244T2/de not_active Expired - Lifetime
- 1998-05-26 EP EP98401244A patent/EP0885872B1/fr not_active Expired - Lifetime
- 1998-05-26 ES ES98401244T patent/ES2167851T3/es not_active Expired - Lifetime
- 1998-06-16 IN IN1305MA1998 patent/IN187756B/en unknown
- 1998-06-16 JP JP10168322A patent/JPH1171322A/ja active Pending
- 1998-06-16 CN CN98109896.7A patent/CN1203220A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0885872A1 (fr) | 1998-12-23 |
ES2167851T3 (es) | 2002-05-16 |
CA2238398A1 (fr) | 1998-12-16 |
ATE209176T1 (de) | 2001-12-15 |
PT885872E (pt) | 2002-04-29 |
FR2764600A1 (fr) | 1998-12-18 |
JPH1171322A (ja) | 1999-03-16 |
IN187756B (fr) | 2002-06-15 |
FR2764600B1 (fr) | 1999-08-20 |
CN1203220A (zh) | 1998-12-30 |
DE69803244T2 (de) | 2002-08-08 |
DE69803244D1 (de) | 2002-02-21 |
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